Catalytic dealkylation of alkyl aromatic compounds



Jan. 27, 1948. w. GILBERT ET AL 2,435,038

` CATALYTIC DEALKYLATION OF ALKYL AROMATIC CCMOUNDS Filed June 13, 1944 WILLIAM L GILBERT CHARLES MMONTGOMERY Patented .-an. 2.7, 1948 y miran stars S PATENT CATALYTIC DEALKYATION F ALKYL l AROMATIC COMPOUNDS Application .time 18,1944, Serial No. 540,066

6 Claims. (Cl. i860-02H) ii This invention relates to an improved process for the catalytic dealkylation of alkyl aromatic compounds and, more particularly, it relates to an improved process for producing phenols and.

olens by the dealkylation of alkylated phenols having at least one alkyl substituent containing three or more carbon atoms.

The dealkylation of alkyl aromatic compoun is a useful method of providing valuable materials for the manufacture of drugs, dyes, plasticizers and the like. The dealkylation of alkyl phenols, in addition to providingsuch useful chemical compounds and intermediates, also provides a process for isolating in pure form certain phenols which cannot be separated from their isomers in the unalkylated form. For example, metaand para-cresol cannot be separated by ordinary means such as by fractional distillation, since there is a dierence of only 0.8 C. in their boiling points. However, by alkylating a commercial mixture of metaand para-cresci with isobutylene, the two products, di-tertiary-butyl meta-cresol and di-tertiary-butyl para-cresol, can be separated by fractional distillation since their boiling points are 17 C. apart. Either or both of the pure cresol isomers can then be produced by debutylating the di-butylated compounds.

Dealkylation of alkyl aromatic compounds such as alkyl phenols can be accomplished either thermally or with the aid of a catalyst. Thermal dealkylation is, in general, ine'icient because at `the temperatures required for dealkylation,

secondary reactions occur which lower the yield of the desired products and form undesirable byproducts which make the recovery and purification of the desired products more diflicult. Known catalytic processes of dealkylating alkyl aromatic compounds using either solid or liquid catalysts also are subject to certain disadvan-` tages.

Processes which use the oxides, suldes and silicates of nickel, iron, aluminum, zinc, barium and cadmium in conjunction withA added hydrogen are difcult and expensive to operate. Acid catalysts such as have been used heretofore in the dealkylation of alkyl phenols are often corrosive to the dealkylation apparatus under conditions of operation. And in general none of the catalysts have been capable of regeneration and re-use at a sumclently low cost nor have they been sufficiently rugged to make their re-use commercially desirable.

It is an object achieved by this invention to provide an improved method for the catalytic dealkylation of alkyl laromatic compounds in which the catalyst used is commercially available at low cost, is non-corrosive to dealkylation apparatus and can be regenerated and re-used repeatedly.

It is more particularly an'object of this invention to provide an efficient vand economical method for the production of phenols and olerlns from alkyl phenols having at least one alkyl substituent containing three or more carbon atoms, by dealkylating said alkyl phenols in the presence of a cheap, readily available, non-corrosive, rugged and re-usablel catalyst which is capable of eecting substantially complete dealkylation of the alkylated phenol without excessive polymerization of the olefin products of the dealkylation.

By the term "dealkylation and the like as used herein and in the appended claims is meant an operation in which relatively large alkyl groups such 'as those containing `three or more carbon atoms are split oi from an alkyl aromatic compound without removing such 4methyl and ethyl groups as may be present.

In accordance with the present invention, it h as been found that the disadvantages heretofore attendant upon the catalytic dealkylation of alkyl-aromatic compounds may be obviated and that alkyl aromatic compounds, such as alkyl phenols, can be dealkylated by contacting such compounds at temperatures above about 200 C.

with active clays. These clay catalysts are readily available and cheap and have little tendency to effect polymerizatiomof the olen products produced, do not cause corrosion of the metal of the aparatus in which the dealkylation is carried out and can be regeneratedand re-used a number of times. y

For example, by contacting an alkyl phenol having one or more alkyl substituents each containing three or more carbon atoms with an active clay at a temperature above about 200 C., dealkylation of the alkyl' phenol and the production of a simple phenol and an olen can be effected .witha minimum of polymerization or other objectionable side reactions. Similarly, by dealkylation of an alkylated aromatic hydrocarbon such as anA alkyl benzene or alkyl naphtha- Iene, by contact with clay above about 200 C., the corresponding aromatic hydrocarbon and olen can be produced with little polymerization or other side reactions. A method is thus provided Which may be used commercially with advantage because substantially no corrosion of the metal parts of the apparatus takes place while commercial rates of reaction comparable with those obtained. for example, with a sulfuric acid dealkylation catalyst, can be maintained.

The active clays which we have found suitable as catalysts for the purposes of our invention include such materials as Georgia clay, lloridin,v

Attapulgus clay. dlatomaceous earth, fullers earth and the like. These clays are customarily used in the form of 30 to Gli-mesh granules, althoughsmaller duid type particles or larger granules or pellets may be used. When these clay catalysts are used fresh their activity is somewhat higher than after repeated use and regeneration. This is evidenced by the fact that after operation with the same catalyst over a relatively long period, the amount of partially dealkylated charge to be found in the products increases somewhat while any tendency to form polymers disappears almost entirely, whereas with fresh catalyst substantially no partially dealkylated charge is obtained and a'small amount of polymer is formed.

The temperatures required for dealkylation using a clay catalyst according to our invention vary with the particular alkylated aromatic compound being treated. In general, temperatures between aboutA 200 and 600 C. are required. Alkyl phenols can be dealkylated with clay cat-alysts at relatively low temperatures within this of such compounds at a temperature of 500 to The time of contact of the alkyl aromatic com- 'pound being dealkylated, with the clay catalyst,

may be regulated to vary the yield of dealkylation products. In vapor phase operation using a fixed bed of clay catalyst at a temperature-of about 200 to 600 C., we have found it particularly advantageous to use space velocities of 0.2 to 3.0. Space velocity as used herein is measured by the volume of liquid charged per hour per volume of catalyst.

The dealkylation of alkyl aromatic compounds, according to our invention. may be carried out in a. variety of ways. For example a xed bed, moving bed, or suspended catalyst may be used. In the accompanying drawing, there is illustrated schematically one form of apparatus for effecting dealkylation in a substantially continuous operation witha fixed catalyst bed, as described hereinafter.

The compound to be dealkylated is introduced through valve i0 and conduit II into a preheater I2 where it'is vaporized and heated to a temperature between 200 and 600 C. Vapors from the pre-heater are then passed through conduit I3 and valve I4 into the top 'of catalyst case l5 which may be filled for example with granular Georgia clay. The temperature of the catalyst is maintained at the desired dealkylation temperature between 200 and 600 C. by suitable means (not shown).

The dealkylation products are conducted from the bottom of catalyst case I5 through valve i8 and conduit I1 to a fractionating column Il where the oleflnic products are taken overhead and are conducted through conduit I8 intolcondenser 20 and receiver 2 I. Reflux for column I8 is provided from the receiver 2| through valve 22, conduit 23. pump 24 and conduit 25 to the head of column I8. The aromatic dealkylation products together with undealkylated materials are taken from the bottom of column I8 through valve 26 and conduit 2l to fractionating column 28 Where they are fractionated, and a pure dealkylated aromatic product ls taken overhead through conduit 28, reboiler 30 and conduit 8| into a receiver 32. Redux for column 28 is provided from the receiver 32 through valve 38, conduit 34, pump 35, and conduit 35 to thetop of column 28. The pure aromatic dealkylation product is collected through conduit 31 in suitable storage means. The bottoms from column 28, which consist largely of undealkylated charge, are recycled through valve 38, conduit 38. collection tank 40, conduit 4|, pump 42, conduit 43 and valve 44 to the inlet feed line The olefinlc distillate from column I8 which has been collected in receiver 2| may be transferred through valve 22, conduit 45, valve 48 and conduit 4l to a stabilizer 48 heated by reboller 30. The distillate from column 48 is conducted through conduit 49 into condenser 50 and is collected in a receiver 5|. Reflux for column 48 is provided through conduit 52, valve 53, pump 54 and conduit 55 to the top of column 48. The pure olefin is conducted from receiver 5I through valve 56 to suitable storage or, for example, to an alkylation unit. The bottoms from column 48 which consist of any polymerization by-prolucts are removed through valve 51 and conduit 58 and collected in tank 58.

When the catalyst in catalyst case I5 has been exhausted, valves I4 and i6 are closed and valve 60 is opened, which admits the charge to alternate catalyst case 5|. The products from catalyst case 6| are conducted through valve B2 and conduit I1 to fractionation tower I8 and the remainder of the apparatus. as before. While the charge is being conducted through catalyst case 6I, the catalyst in case I5 may be regenerated by introducing a regeneration gas consisting of air and ue gas through valve 63 and conduit 64 into the top of catalyst case I5. Products of regeneration are discharged through conduit 55, valve 68 and conduit 51. Alternatively, the catalyst contained in case 5 may be removed for regeneration and replaced at onceby fresh catalyst. When catalyst case I5 has been regenerated, the charge may again be introduced into the top of case I5 by opening valve I4 and closing valve 60 and the vproducts conducted from the bottom of case I5 through valve i8 and conduit I1 to fractionation tower I5. Catalyst case 6I may then be regenerated by introducing regeneration gases into the top of the tower through valve 68 and conduit 69 and conducting the regeneration gases out through conduit 10, valve 1| and conduit 61.

Thus. by use of this apparatus in which alternate catalyst cases are provided, substantially continuous operation can be effected with good yields of pure olein and pure aromatic compounds.

In the following specic examples, there are illustrated the results obtainable by the dealkylatlon of alkyl aromatic compounds according to the method of our invention using active clay catalysts at temperatures betweenl 200l and 600 C. A

EXAMPLE I In this example, di-tertiary-butyl metacresol was dealkylated by contacting the di-butyl-meta.- cresol with fresh Georgia clay at a temperature of 260 C. and at various space velocities between 0.2 and 3.0. The following table illustrates in runs 1-4 the results obtained at the respective space velocities. In column 5 of Table I, there are also shown the results obtained in the debutylation of di-tertiary-butyl para-cresol at a temperature of 260 C. and space. velocity of 0.42.

6 In these results, as in the prior results shown in Table I.' dealkylation was substantially complete, and no detectable amount of mono-tertiarybutyl meta-cresol was found in the products. However, a, saturating effect was/observed in the olefin fraction. `As higher temperatures were.

used, increasing amounts of the isobutylene productk are converted to isobutane. From these results, it will be apparent that when it is desired to obtain olenic products without conversion to parafllns, temperatures not substantially above 260 C. are most desirable. On the other hand,

l if it is desired to obtain a substantial proportion of saturated isoparaii'in in the products, higher temperaturesare effective to produce a mixture Table I of isobutane with isobutylene.

Run No 1 2 a i 5 Exmrrn III Tem @rature C 25o 26o 25o 2te 25o spacgvelocity a 0.23 0.65 1 00 2 ,3 l 42 20 In this example. the effectiveness 0f the proc goeden?, wt. percent 93.5 91.5 95.5 98.5 102.2 GSS 0f fllrhmvent On in ithldetalkyltln of alkyl ro uc: aromat c ydrocarbons s us rate Amyl en- Cresol,wt. er cent of ch 47.9 45.7 47.2 49.2 48.2 Polymer, wt). per cent of hg. 2. 5 3. 6 3. 9 2. 9 3. 2 zene, ternary-butyl benzene. (ii-ethyl benzene and isobutylene, wt.per cent of chg 43.2 42.2 43.2 46.4 49.0 cumene were dealkylated by contacting with Yield. per cent of theoretical: o

cresol 97.5 95. 1y 95.4 93.2 98.5- 25 Georgia clay at temperatures between 350 and Butylene c.+po1ymer) 90.0 92.4 92.5 ses 102.8 500 C. The results of these tests are shown in the following Table III.

Table III RunNo 1 2 3 4 5 o Charge Amyl Benzene.. Amyi Benzene.. t-Butyl Benzene tButylBenzene Di Ethyl Benzene... Cumene Temperature, C 400 500 500 350 540 500. Space Velocity 0.25 0. 0.25 Dea1kylstion,mol.per cent- 28.2. 52.9 84.3

EXAMPLE II In this example, 'dealkylation of di-tertiarybutyl meta-cresol was 4carried out with a fresh Georgia clay catalyst at a variety of temperatures higher than 260 C. and a fixed space velocity of about 0.23. The results of these runs are shown in the following Table II.

Table II Run No l Temperature, "C 2 Space Velocity, liq Products, wt. per cent of charge:

Liquid Cond. Gas Loss, wt. per cent Anal. of condsas, mol. per ce Air and C i loco Cri-upsets From the data here obtained, it will be observed that effective dealkylation of such compounds is also obtainable according to the method of our invention. These tests also show evidence of the saturating effect observed in connection with the dealkylation of alkyl phenols at higher temperatures. For example, in runs 1 and 2 the C5 fractions contained approximately 10 per cent pentanes and the gas from runs 3 and 4 contain 2 to 3 per cent of isobutane. No propane was found in the gas obtained 1from the dealkylation of cumene.

1 While our invention has been described herein in detail with respect to certain speciiic embodiments thereof, it is to be understood that the invention is not limited to the details of such embodiments except as hereinafter defined inthe appended claims.

What We claim is:

1. A process for producingv isobutylene which comprises contacting a mono-hydric tertiarybutyl phenol with an active clay catalyst at a temperature between about 250 C. and about 300 C.

2. A process for producing isobutylene which comprises contacting a tertiary-butyl cresol with an active clay catalyst at a temperature between about 250 C. and about 300 C.

3. A process for producing isobutylene which comprises contacting a di-(tertiary-butyl) -cresol with an active vclay catalyst at a temperature between about 250" C. and about 300 C.

4. A process for producing isobutylene which comprises v contacting a mono-(tertiary-butyl) cresol with an active clay catalyst at a, temperature between about 250 C. and about 350 C.

5. A process for producing isobutylene which comprises contacting dl- (tertiary-butyl) meta.

oresol with an active clay catalyst at a temperature between about 250 C. and about 300' C.

6. A process for producing isobutyiene which comprises contacting di-(tertiary-butyl) -meta-` REFERENCES CITED The following references are of record in the ie of this patent:

Number UNITED STATES PATENTS Name Date Schollkopf Feb, 18, 1930 Sachanen et ai Mar. 19, 1940 Sachanen et a1. (A) Nov. 26, 1940 Sachanen et a1. (B) Nov. 26, 1940 Stevens July. 21, 1942 Meharg et ai. Sept. I5, 1942 Meharg Sept. 15, 1942 Stevens et al Aug. 241943 

